Cosmetic compositions

ABSTRACT

A make-up composition in the form of water-in-oil or oil-in-water emulsion comprising an acidic anti-active dissolved in the aqueous phase and a pigment or mixture of pigments dispersed in the oil phase. The make-up composition exhibits anti-effectiveness and product and color stability.

FIELD OF THE INVENTION

This application is a 371 of PCT/US 94/08615, filed on Aug. 1, 1994.

The present invention relates to cosmetic compositions and moreparticularly, to pigmented foundation make-up compositions andconcealers having anti-acne activity and formulation and colourstability.

BACKGROUND OF THE INVENTION

A foundation composition can be applied to the face and other parts ofthe body to even skin tone and texture and to hide pores, imperfections,fine lines and the like. A foundation composition is also applied tomoisturize the skin, to balance the oil level of the skin and to provideprotection against the adverse effects of sunlight, wind and the harshenvironment.

Make-up compositions are generally available in the form of liquid orcream suspensions, emulsions, gels, pressed powders or anhydrous oil andwax compositions.

U.S. Pat. No. 3,444,291 discloses a method of filling and camouflagingskin cavities by applying a composition which includes 65 to 75 parts byweight of a microcrystalline wax and about 25 to 35 parts of a mineraloil. The composition includes a colourant, preferably a coal tar dye,for example, D&C Red No. 17, which matches the colour of the user'sskin.

A spreadable, flowable and greaseless cosmetic cover-up composition istaught in U.S. Pat. No. 4,486,405. That composition is characterized bythe presence of a first and a second alkoxylated surfactant present insubstantially the same concentration.

U.S. Pat. No. 4,804,532 recites a facial cosmetic powder which utilizescrystalline silica in much lower concentration than that employed in thethen prior art compositions. This powder, used as a blush or a facialcoating, is said to be effective in hiding skin wrinkles, lines andpores. The composition is a mixture of a colour phase and a diluentphase. The colour phase is formed by blending crystalline silica withcolourants. The resultant colour phase is mixed with the diluent phase,essentially formed from nacreous materials such as talc and mica, toform the composition.

The use of a foundation composition which has a significantly highconcentration of nacreous material is taught in U.S. Pat. No. 3,978,207.This foundation, a pressed powder composition, is characterized by thepresence of a nacreous material such as mica and a binder oil whichprovides a frosted pearl effect, that is, a lustrous look. The colour ofthis foundation is provided by the nacreous material.

U.S. Pat. No. 4,659,562 discloses a cosmetic make-up composition whichincludes, as a binding agent therefore, an intimate mixture of from 5 to95 weight percent of a mixture of finely divided silica and about 5 to95 weight percent of finely divided polyethylene fibres. The compositionis recited to maintain its uniformity over the areas of the skin towhich it is applied. That is, it is said to be "creaseproof". Thecomposition of the '562 patent includes colourant in admixture withnacreous agents.

Nakamura et al., Preprints of the XIVth I.F.S.C.C. Congress, Barcelona,1986, Vol. I, 51-63 (1986) describes a novel make-up compositionutilizing spherical silica and polydimethyl siloxane. This combinationis recited to provide a foundation which reduces wrinkle visibility to agreater extent than make-up foundations with which it was compared. Thisreduction in wrinkle visibility is caused by optical blurring enhancedby the novel use of spherical silica and polydimethyl siloxane.

U.S. Pat. No. 5,143,722 discloses a cosmetic make-up compositioncomprising water-in-oil emulsions comprising pigment coated withpolysiloxane, a silicone phase, a water phase and apolydiorganosiloxane-polyoxyalkylene copolymeric surfactant.

Foundations in the form of water-in-oil emulsions are well known andprovide good coverage and good skin feel, wear and appearance. At thesame time, it would be desirable to provide a foundation compositionhaving topical anti-acne activity. There are many compounds which areknown to exhibit anti-acne properties when applied topically to theskin. A commonly used keratolytic agent having anti-acne activity issalicylic acid. As salicylic acid is virtually insoluble in water it isdifficult to incorporate into the aqueous phase of an emulsioncomposition. Delivery of salicylic acid from the pigment-containing oilphase of an emulsion foundation composition can, however, lead todiscolouration of the composition due to interaction between thesalicylic acid and pigments, especially of the iron oxide type. It wouldtherefore be desirable to deliver the salicylic acid in soluble formfrom the aqueous phase.

Polyvinylpyrrolidone is known for use as a solubilizing/complexing agentin a variety of compositions.

GB-A-2,041,963 discloses an aqueous detergent composition for cleansingoily skin comprising a water-soluble salt of an N-acyl ester ofsarcosine, a polyvinylpyrrolidone cosolubilizer and a protein and/orprotein hydrolysate. The composition can also contain salicylic acid asa keratolytic agent and a buffer such as citric acid/citrate. There isno disclosure, however, of cosmetic compositions containing solubilizedacidic anti-acne actives in fully protonated form as specified herein.

Since acidic anti-acne agents are most active at low pH (when a highconcentration of free acid is present in solution) it would be desirableto deliver the agent from an aqueous phase at a pH at which it existssignificantly in protonated form. It is accordingly a primary object ofthis invention to provide a cosmetic composition comprising a low pHaqueous solution of an anti-acne active.

It is also an object of the invention to provide a cosmetic compositionhaving improved anti-acne activity and stability.

It is a further object of the invention to provide a cosmeticcomposition in the form of an oil-in-water or water-in-oil emulsionhaving improved colour stability and pigment/anti-acne activecompatibility.

SUMMARY OF THE INVENTION

In accordance with one aspect of the present invention, there isprovided a cosmetic composition in the form of an emulsion, gel orlotion comprising an aqueous/alcoholic solution of an acidic anti-acneactive and a pyrrolidone-based complexing agent therefor, and whereinthe aqueous/alcoholic solution has a pH of less than about pK_(a) +1,where pK_(a) is the logarithmic acidity constant for the fullyprotonated anti-acne active.

The cosmetic compositions of the present invention provide anti-acneefficacy together with improved product and colour stability.

According to another aspect of the present invention there is provided amake-up composition in the form of a water-in-oil or oil-in-wateremulsion comprising an acidic anti-acne active dissolved in the aqueousphase and a pigment or mixture of pigments dispersed in the oil phase.

All levels and ratios are by weight of total composition, unlessotherwise indicated. Chain length and degrees of alkoxylation are alsospecified on a weight average basis.

DETAILED DESCRIPTION OF THE INVENTION

The cosmetic composition according to one aspect of the presentinvention comprises an aqueous/alcoholic solution of an acidic anti-acneactive and a pyrrolidone-based complexing agent. The composition is inthe form of an emulsion, gel or lotion.

According to this first aspect of the present invention a firstessential component is an aqueous/alcoholic solution of an anti-acneactive. Suitable anti-acne actives for use herein include salicylicacid, retinoic acid and its derivatives, azelaic acid and itsderivatives, lactic acid, glycolic acid, pyruvic acid, flavonoids, andmixtures thereof.

The anti-acne active used in the composition herein is preferablyselected from salicylic acid and azelaic acid, and mixtures thereof,more preferably salicyclic acid. The anti-acne active is present at alevel of from about 0.1% to about 10%, preferably from about 0.1% toabout 5%, more preferably from about 0.5% to about 3%, by weight ofcomposition.

The anti-acne active is solubilized in water or an alcoholic solution,for example, solutions based upon C₂ -C₆ alcohols, diols and polyols,preferred alcohols being selected from ethanol, dipropylene glycol,butylene glycol, hexylene glycol, and mixtures thereof. Alcohol ispreferably present in the compositions herein at a level of from about1% to about 20%. The final aqueous/alcoholic anti-acne active solutionpreferably has a pH at ambient temperature (25° C.) of less than aboutpK_(a) +1, where pK_(a) is the logarithmic acidity constant for thefully protonated anti-acne active. In preferred embodiments, the pH ofthe final solution is less than about pK_(a).

The logarithmic acidity constant is thus defined by reference to theequilibrium

    H.sup.+ +H.sub.n-1 A=H.sub.n A

where H_(n) A is the fully protonated acid, n is the number of protonsin the fully protonated acid and H_(n-1) A is the conjugate base of theacid corresponding to loss of one proton.

The acidity constant for this equilibrium is therefore ##EQU1##

For the purposes of this specification, acidity constants are defined at25° C. and at zero ionic strength. Literature values are taken wherepossible (see Stability Constants of Metal-Ion Complexes, SpecialPublication No. 25, The Chemical Society, London); where doubt arisesthey are determined by potentiometric titration using a glass electrode.

The pK_(a) of the acidic anti-acne active used herein is preferably inthe range of from about 1 to about 6, more preferably from about 1 toabout 4.5, especially from about 1.5 to about 4.0.

The pH of the final aqueous/alcoholic anti-acne active solution ispreferably in the range of from about 1 to about 7, more preferably fromabout 2 to about 5, especially from about 2 to about 4. At pH values ofless than about 5 the aqueous phase is preferably free of acid labilespecies such as acrylic acid/ethyl acrylate copolymers andpolyglycerylmethacrylate.

A second essential component of the compositions of the first aspect ofthe present invention is a pyrrolidone-based complexing agent.

The pyrrolidone-based complexing agent is useful herein from theviewpoint of aiding solubilization of the anti-acne active. Thepyrrolidone-based complexing agent used herein is preferably selectedfrom polyvinylpyrrolidone complexing agents or C₁ -C₄ alkylpolyvinylpyrrolidone complexing agents having a molecular weight(viscosity average) in the range from about 1500 to about 1,500,000,preferably from about 3000 to about 700,000, more preferably from about5000 to about 100,000. Suitable examples of pyrrolidone-based complexingagents are polyvinylpyrrolidone (PVP) (or povidone) and butylatedpolyvinylpyrrolidone. The most preferred pyrrolidone-based complexingagent herein is a polyvinylpyrrolidone complexing agent. PVP iscommercially available under the trade name Luviskol (RTM) from BASF. Apreferred PVP complexing agent herein is Luviskol K17 which has aviscosity-average molecular weight of about 9,000. Otherpyrrolidone-based complexing agents for use herein include C₁ -C₁₈ alkylor hydroxyalkyl pyrrolidones such as lauryl pyrrolidone.

The pyrrolidone-based complexing agent is present in the compositionherein in a level of from about 0.1% to about 10%, preferably from about0.1% to about 5% by weight of composition. The weight ratio of anti-acneactive:pyrrolidone-based complexing agent is in the range from about10:1 to about 1:10, preferably from about 5:1 to about 1:5.

Preferred embodiments of the invention additionally comprise from about0.01% to about 5% by weight of an acid or salt thereof which is solublein water at pH values of less than or equal to the pK_(a) of thecorresponding acid, for example, an acid selected from citric acid,boric acid, and salts, and mixtures thereof. These materials arevaluable herein in combination with the pyrrolidone-based complexingagent from the viewpoint of aiding solubilization of the anti-acneactive. Particularly preferred herein from this viewpoint is a sodiumsalt of citric acid. In preferred embodiments, the acid or salt thereofis soluble to a level of at least 5% w/w at 25° C.

The composition of the present invention can be in emulsion (w/o oro/w), gel or lotion form but is preferably in the form of a water-in-oilemulsion, wherein in preferred embodiments the oil phase comprises amixture of volatile silicones and non-volatile silicones. The siliconeoil is present in an amount of from about 1% to about 50% by weight.Suitable volatile silicone oils include cyclic and linear volatilepolyorganosiloxanes (as used herein, "volatile" refers to thosematerials which have a measurable vapour pressure at ambientconditions).

A description of various volatile silicones is found in Todd, et al.."Volatile Silicone Fluids for Cosmetics", 91 Cosmetics and Toiletries27-32 (1976).

Preferred cyclic silicones include polydimethylsiloxanes containing fromabout 3 to about 9 silicon atoms, preferably containing from about 4 toabout 5 silicon atoms. Preferred linear silicone oils include thepolydimethylsiloxanes containing from about 3 to about 9 silicon atoms.The linear volatile silicones generally have viscosities of less thanabout 5 centistokes at 25° C., while the cyclic materials haveviscosities of less than about 10 centistokes. Examples of silicone oilsuseful in the present invention include: Dow Corning 344, Dow Corning21330, Dow Corning 345, and Dow Corning 200 (manufactured by the DowCorning Corporation): Silicone 7207 and Silicone 7158 (manufactured bythe Union Carbide Corporation). SF:202 (manufactured by GeneralElectric) and SWS-03314 (manufactured by Stauffer Chemical).

Suitable non-volatile silicones preferably have an average viscosity offrom about 1,000 to about 2,000,000 mm².s⁻¹ at 25° C. more preferablyfrom about 10,000 to about 1,800,000 mm².s⁻¹, even more preferably fromabout 100,000 to about 1,500,000 mm².s⁻¹. Lower viscosity non-volatilesilicone conditioning agents, however, can also be used. Viscosity canbe measured by means of a glass capillary viscometer as set forth in DowCorning Corporate Test Method CTM0004, Jul. 20, 1970. Suitablenon-volatile silicone fluids for use herein include polyalkyl siloxanes,polyaryl siloxanes, polyalkylaryl siloxanes, polysiloxanes with aminofunctional substitutions, polyether siloxane copolymers, and mixturesthereof. The siloxanes useful in the present invention may be endcappedwith any number of moieties, including, for example, methyl, hydroxyl,ethylene oxide, propylene oxide, amino and carboxyl. However, othersilicone fluids having skin conditioning properties may be used. Thenon-volatile polyalkyl siloxane fluids that may be used include, forexample, polydimethylsiloxanes. These siloxanes are available, forexample, from the General Electric Company as a Viscasil (RTM) seriesand from Dow Corning as the Dow Corning 200 series. Preferably, theviscosity ranges from about 10 mm².s⁻¹ to about 100,000 mm².s⁻¹ at 25°C. The polyalkylaryl siloxane fluids that may be used, also include, forexample, polymethylphenylsiloxanes. These siloxanes are available, forexample, from the General Electric Company as SF 1075 methyl phenylfluid or from Dow Corning as 556 Cosmetic Grade Fluid. The polyethersiloxane copolymer that may be used includes, for example, apolypropylene oxide modified dimethylpolysiloxane (e.g., Dow CorningDC-1248) although ethylene oxide or mixtures of ethylene oxide andpropylene oxide may also be used.

References disclosing suitable silicone fluids include U.S. Pat. No.2,826,551, Green; U.S. Pat. No. 3,964,500, Drakoff, issued Jun. 22nd,1976; U.S. Pat. No. 4,364,837, Pader; and GB-A-849,433, Woolston. Inaddition, Silicone Compounds distributed by Petrarch Systems Inc., 1984provides an extensive (though not exclusive) listing of suitablesilicone fluids.

Preferred non-volatile silicones for use herein includepolydiorganosiloxane-polyoxyalkylene copolymers containing at least onepolydiorganosiloxane segment and at least one polyoxyalkylene segment,said polydiorganosiloxane segment consisting essentially of

    R.sub.b SiO.sub.(4-b)/2

siloxane units wherein b has a value of from about 0 to about 3,inclusive, there being an average value of approximately 2 R radicalsper silicon for all siloxane units in the copolymer, and R denotes aradical selected from methyl, ethyl, vinyl, phenyl and a divalentradical bonding said polyoxyalkylene segment to the polydiorganosiloxanesegment, at least about 95% of all R radicals being methyl; and saidpolyoxyalkylene segment having an average molecular weight of at leastabout 1000 and consisting of from about 0 to about 50 mol percentpolyoxypropylene units and from about 50 to about 100 mol percentpolyoxyethylene units, at least one terminal portion of saidpolyoxyalkylene segment being bonded to said polydiorganosiloxanesegment, any terminal portion of said polyoxyalkylene segment not bondedto said polydiorganosiloxane segment being satisfied by a terminatingradical; the weight ratio of polydiorganosiloxane segments topolyoxyalkylene segments in said copolymer having a value of from about2 to about 8. Such polymers are described in U.S. Pat. No. 4,268,499.

More preferred for use herein are polydiorganosiloxane-polyoxyalkylenecopolymers having the general formula: ##STR1## wherein x and y areselected such that the weight ratio of polydiorganosiloxane segments topolyoxalkylene segments is from about 2 to about 8, the mol ratio ofa:(a+b) is from about 0.5 to about 1, and R is a chain terminatinggroup, especially selected from hydrogen; hydroxyl; alkyl, such asmethyl, ethyl, propyl, butyl, benzyl; aryl, such as phenyl; alkoxy suchas methoxy, ethoxy, propoxy, butoxy; benzyloxy; aryloxy, such asphenoxy; alkenyloxy, such as vinyloxy and allyloxy; acyloxy, such asacetoxy, acryloxy and propionoxy and amino, such as dimethylamino.

The number of and average molecular weights of the segments in thecopolymer are such that the weight ratio of polydiorganosiloxanesegments to polyoxyalkylene segments in the copolymer is preferably fromabout 2.5 to about 4.0.

Suitable copolymers are available commercially under the tradenamesBelsil (RTM) from Wacker-Chemie GmbH, Geschaftsbereich S, PostfachD-8000 Munich 22 and Abil (RTM) from Th. Goldschmidt Ltd,. Tego House,Victoria Road, Ruislip, Middlesex, HA4 OYL. Particularly preferred foruse herein are Belsil (RTM) 6031, Abil (RTM) B88183 and DC3225C. Apreferred silicone herein is known by its CTFA designation asdimethicone copolyol.

The silicone oil phase preferably comprises from about 2% to about 25%,more preferably from about 5% to about 15% by weight of composition ofnon-volatile silicones.

A highly preferred component of the compositions herein is a humectantor mixture of humectants. The humectant or mixture of humectants hereinis present in an amount of from about 0.1% to about 30% preferably fromabout 5% to about 25%, and more preferably from about 10% to about 20%by weight of composition. Suitable humectants are selected fromglycerine and polyglycerylmethacrylate lubricant having a viscosity at25° C. of 300,000 to 1,100,000 cps; a specific gravity at 25° C. of 1 to1.2 g/ml, a pH of 5.0 to 5.5; a bound water content of 33 to 58%; and, afree water content from 5 to 20%.

The humectant can be incorporated at least partly into the oil phase ofthe water-in-oil emulsion so as to form a multiphasehumectant-in-oil-in-water dispersion. The oil phase preferably comprisesfrom about 0.1% to about 10%, more preferably from about 0.1% to about3% by weight of humectant on a composition basis. The humectant can beintroduced into the oil phase in the form of a mixture with orincorporated within a particulate lipophilic or hydrophobic carriermaterial.

Polyglycerylmethacrylate lubricants having the desired properties aremarketed by Guardian Chemical Corporation under the trademark"Lubrajel". The "Lubrajels" identified as "Lubrajel DV", "Lubrajel MS",and "Lubrajel CG" are preferred in the present invention. The gellingagents sold under these trademarks contain about 1% propylene glycol.

Other suitable humectants include sorbitol, panthenols, propyleneglycol, butylene glycol, hexylene glycol, alkoxylated glucosederivatives, such as Glucam (RTM) E-20, hexanetriol, and glucose ethers,and mixtures thereof. Urea is also suitably added as a humectant in theinternal aqueous phase.

The panthenol moisturiser can be selected from D-panthenol (R!-2,4-dihydroxy-N- 3-hydroxypropyl)!-3,3-dimethylbutamide),DL-panthenol, calcium pantothenate, royal jelly, panthetine,pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyllactose and Vitamin B complex.

The preferred humectant herein is glycerine. Chemically, glycerine is1,2,3-propanetriol and is a product of commerce.

Preferred embodiments herein comprise a pigment or mixture of pigments.Suitable pigments for use herein can be inorganic and/or organic. Alsoincluded within the term pigment are materials having a low colour orlustre such as matte finishing agents, and also light scattering agents.Examples of suitable pigments are iron oxides, acylglutamate ironoxides, ultramarine blue, D&C dyes, carmine, and mixtures thereof.Depending upon the type of make-up composition, eg. foundation orblusher, a mixture of pigments will normally be used.

It is a feature of the composition herein that the pigment and anti-acneactive have excellent overall compatability and colour stability. Thusaccording to another aspect of the present invention there is provided amake-up composition in the form of a water-in-oil or oil-in-wateremulsion comprising an acidic anti-acne active dissolved in the aqueousphase and a pigment or mixture of pigments dispersed in the oil phase.

The foundation composition can also include at least one matte finishingagent. The function of the matte finishing agent is to hide skin defectsand reduce shine. Such cosmetically acceptable inorganic agents, i.e.,those included in the CTFA Cosmetic Ingredient Dictionary, Third Ed., assilica, hydrated silica, silicone-treated silica beads, mica, talc,polyethylene, titanium dioxide, bentonite, hectorite, kaolin, chalk,diatomaceous earth, attapulgite zinc oxide and the like may be utilized.Of particular usefulness as a matte finishing agent is low lustrepigment such as titanated mica (mica coated with titanium dioxide)coated with barium sulfate. Of the inorganic components useful as amatte finishing agent low lustre pigment, talc, polyethylene, hydratedsilica, kaolin, titanium dioxide and mixtures thereof are particularlypreferred. Materials suitable for use herein as light-scattering agentscan be generally described as spherical shaped inorganic materialshaving a particle size of up to about 100 microns, preferably from about5 to about 50 microns, for example spherical silica particles.

The total concentration of the pigment may be from about 0.1 to about25% by weight and is preferably from about 1 to about 10% by weight ofthe total composition, the exact concentration being dependent to someextent upon the specific mixture of pigments selected for use in afoundation make-up or blusher to achieve the desired shades. Thepreferred compositions contain from about 2% to about 20% by weight oftitanium dioxide and most preferably from about 5% to about 10% byweight of titanium dioxide.

The preferred pigments for use herein from the viewpoint ofmoisturisation, skin feel, skin appearance and emulsion compatibilityare treated pigments. The pigments can be treated with compounds such asamino acids such as lysine, silicones, lauroyl, collagen, polyethylene,lecithin and ester oils. The more preferred pigments are the silicone(polysiloxane) treated pigments.

The balance of the composition of the present invention is deionizedwater. The composition preferably comprises from about 30% to about 95%,more preferably from about 40% to about 80% by weight of the oil phase,and from about 5% to about 70%, more preferably from about 20% to about60% by weight of the water phase.

The make-up compositions of the present invention can also comprise aparticulate cross-linked hydrophobic acrylate or methacrylate copolymer.This copolymer is particularly valuable for reducing shine andcontrolling oil while helping to provide effective moisturizationbenefits. The cross-linked hydrophobic polymer is preferably in the formof a copolymer lattice with at least one active ingredient disperseduniformly throughout and entrapped within the copolymer lattice.Alternatively, the hydrophobic polymer can take the form of a porousparticle having a surface area (N₂ -BET) in the range from about 50 to500, preferably 100 to 300 m² /g and having the active ingredientabsorbed therein.

The cross-linked hydrophobic polymer when used herein is in an amount offrom about 0.1% to about 10% by weight and is preferably incorporated inthe external silicone-containing oil phase. The active ingredient can beone or more or a mixture of skin compatible oils, skin compatiblehumectants, emollients, moisturizing agents and sunscreens. The polymermaterial is in the form of a powder, the powder being a combined systemof particles. The system of powder particles forms a lattice whichincludes unit particles of less than about one micron in averagediameter, agglomerates of fused unit particles of sized in the range ofabout 20 to 100 microns in average diameter and aggregates of clustersof fused agglomerates of sizes in the range of about 200 to 1,200microns in average diameter.

The powder material of the present invention which can be employed asthe carrier for the active ingredient can be broadly described as across-linked "post absorbed" hydrophobic polymer lattice. The powderpreferably has entrapped and dispersed therein, an active which may bein the form of a solid, liquid or gas. The lattice is in particulateform and constitutes free flowing discrete solid particles when loadedwith the active material. The lattice may contain a predeterminedquantity of the active material. The polymer has the structural formula:##STR2## where the ratio of x to y is 80:20, R' is --CH₂ CH₂ -- and R"is --(CH₂)₁₁ CH₃.

The hydrophobic polymer is a highly crosslinked polymer, moreparticularly a highly cross-linked polymethacrylate copolymer. Thematerial is manufactured by the Dow Corning Corporation, Midland. Mich.,USA, and sold under the trademark POLYTRAP (RTM). It is an ultralightfree-flowing white powder and the particles are capable of absorbinghigh levels of lipophilic liquids and some hydrophilic liquids while atthe same time maintaining a free-flowing powder character. The powderstructure consists of a lattice of unit particles less than one micronthat are fused into agglomerates of 20 to 100 microns and theagglomerates are loosely clustered into macro-particles or aggregates ofabout 200 to about 1200 micron size. The polymer powder is capable ofcontaining as much as four times its weight of fluids, emulsions,dispersions or melted solids.

Adsorption of actives onto the polymer powder can be accomplished usinga stainless steel mixing bowl and a spoon, wherein the active is addedto the powder and the spoon is used to gently fold the active into thepolymer powder. Low viscosity fluids may be adsorbed by addition of thefluids to a sealable vessel containing the polymer and then tumbling thematerials until a consistency is achieved. More elaborate blendingequipment such as ribbon or twin cone blenders can also be employed. Thepreferred active ingredient for use herein is glycerine. Preferably, theweight ratio of humectant: carrier is from about 1:4 to about 3:1.

Also suitable as a highly cross-linked polymethacrylate copolymer isMicrosponges 5647. This takes the form of generally spherical particlesof cross-linked hydrophobic polymer having a pore size of from about0.01 to about 0.05 μm and a surface area of 200-300 m² /g. Again, it ispreferably loaded with humectant in the levels described above.

The compositions of the invention can also contain a hydrophilic gellingagent at a level preferably from about 0.01% to about 10%, morepreferably from about 0.02% to about 2%, and especially from about 0.02%to about 0.5%. The gelling agent preferably has a viscosity (1% aqueoussolution, 20° C., Brookfield RVT) of at least about 4000 mPa.s, morepreferably at least about 10,000 mPa.s and especially at least 50,000mPa.s.

Suitable hydrophilic gelling agents can generally be described aswater-soluble or colloidally water-soluble polymers, and includecellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose,hydroxypropylmethyl cellulose), polyvinylalcohol, polyquaternium-10,guar gum, hydroxypropyl guar gum and xanthan gum.

Among suitable hydrophilic gelling agents are acrylic acid/ethylacrylate copolymers and the carboxyvinyl polymers sold by the B. F.Goodrich Company under the trade mark of Carbopol resins. These resinsconsist essentially of a colloidally water-soluble polyalkenyl polyethercrosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00%of a crosslinking agent such as for example polyallyl sucrose orpolyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940,Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934is a water-soluble polymer of acrylic acid crosslinked with about 1% ofa polyallyl ether of sucrose having an average of about 5.8 allyl groupsfor each sucrose molecule. Also suitable for use herein arehydrophobically-modified cross-linked polymers of acrylic acid havingamphipathic properties available under the Trade Name Carbopol 1382,Carbopol 1342 and Pemulen TR-1 (CTFA Designation: Acrylates/10-30 AlkylAcrylate Crosspolymer). A combination of the polyalkenyl polyethercross-linked acrylic acid polymer and the hydrophobically modifiedcross-linked acrylic acid polymer is also suitable for use herein. Othersuitable gelling agents suitable for use herein are oleogels such astrihydroxystearin and aluminium magnesium hydroxy stearate. The gellingagents herein are particularly valuable for providing excellentstability characteristics over both normal and elevated temperatures.

Neutralizing agents suitable for use in neutralizing acidic groupcontaining hydrophilic gelling agents herein include sodium hydroxide,potassium hydroxide, ammonium hydroxide, monoethanolamine,diethanolamine and triethanolamine.

The make-up compositions herein can additionally comprise an emollient.Emollients suitable for the compositions of the present inventioninclude natural and synthetic oils selected from mineral, vegetable, andanimal oils, fats and waxes, fatty acid esters, fatty alcohols, alkyleneglycol and polyalkylene glycol ethers and esters, fatty acids andmixtures thereof.

Suitable emollients for use herein include, for example, optionallyhydroxy-substituted C₈ -C₅₀ unsaturated fatty acids and esters thereof,C₁ -C₂₄ esters of C₈ -C₃₀ saturated fatty acids such as isopropylmyristate, cetyl palmitate and octyldodecylmyristate (Wickenol 142),beeswax, saturated and unsaturated fatty alcohols such as behenylalcohol and cetyl alcohol, hydrocarbons such as mineral oils, petrolatumand squalane, fatty sorbitan esters (see U.S. Pat. No. 3,988,255,Seiden, issued Oct. 26, 1976), lanolin and lanolin derivatives, such aslanolin alcohol ethoxylated, hydroxylated and acetylated lanolins,cholesterol and derivatives thereof, animal and vegetable triglyceridessuch as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil,oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds,rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil,castor oil, soybean oil, avocado oil, safflower oil, coconut oil,hazelnut oil, olive oil, grapeseed oil, and sunflower seed oil and C₁-C₂₄ esters of dimer and trimer acids such as diisopropyl dimerate,diisostearylmalate, diisostearyldimerate and triisostearyltrimerate.

Preferred emollients are selected from hydrocarbons such asisohexadecane, mineral oils, petrolatum and squalane, lanolin alcohol,and stearyl alcohol. These emollients may be used independently or inmixtures and may be present in the composition of the present inventionin an amount from about 1% to about 30% by weight, and preferably arepresent in an amount from about 5% to about 15% by weight of the totalcomposition.

The composition may also contain additional materials such as, forexample, fragrances, fillers such as nylon, sun-screens, preservatives,electrolytes such as sodium chloride, proteins, antioxidants, chelatingagents and water-in-oil emulsifiers as appropriate.

Another optional component of the make-up composition is one or moreultraviolet absorbing agents. Ultraviolet absorbing agents, oftendescribed as sunscreening agents, can be present in a concentration inthe range of between about 1% and about 12% by weight, based on thetotal weight of composition. Preferably, the UV absorbing agentsconstitute between about 2% and 8% by weight. More preferably, the UVabsorbing agents can be present in the composition in a concentrationrange of between about 4% and about 6% by weight. Of the ultravioletabsorbing agents suitable for use herein, benzophenone-3, octyl dimethylPABA (Padimate O) and mixtures thereof are particularly preferred.

Another optional but preferred component herein is one or moreadditional chelating agents, preferably in the range of from about 0.02%to about 0.10% by weight, based on the total weight of the composition.Preferably, the chelating agent is present in a concentration in therange of between about 0.03% and about 0.07% by weight, based on thetotal weight of the composition. Among the chelating agents that may beincluded in the composition is tetrasodium EDTA.

Another optional but preferred component of the foundation compositionis one or more preservatives. The preservative concentration in thefoundation composition, based on the total weight of that composition,is in the range of between about 0.05% and about 0.8% by weight,preferably between about 0.1% and about 0.3% by weight. Suitablepreservatives for use herein include sodium benzoate and propyl paraben,and mixtures thereof.

The make-up compositions of the present invention can be in the form offoundations, blushers, concealers, compact powders, and the like,preferably as foundations and concealers.

The following Table is provided to illustrate compositions of themake-up of the present invention:

    ______________________________________               I      II     III  IV   V    VI   VII    Example    Wt %   Wt %   Wt % Wt % Wt % Wt % Wt %    ______________________________________    A.    Cetyloctanoate               2.00   0.0    0.0  0.0  0.0  0.0  2.0    Cyclomethicone               8.57   12.25  12.25                                  15.0 12.0 8.57 8.57    Cyclomethicone/    dimethicone    copolyol (90:10)               17.16  20.0   20.0 5.0  8.0  10.0 17.16    Propylparaben               0.75   0.75   0.0  0.75 0.0  0.75 0.75    (33%) in    laureth-7    Dimethicone               2.0    0.0    2.0  3.0  5.0  10.0 0.0    Fluid    Benzophenene-3               0.0    0.0    0.0  0.0  0.0  2.0  0.0    Propylene glycol    Dicaprylate/               0.0    0.0    0.0  5.0  0.0  10.0 0.0    Dicaprate    B.    Titanium Dioxide               8.25   6.0    1.5  6.0  8.0  20.0 8.25    Titanium Dioxide               0.25   0.5    3.0  0.25 0.25 0.0  0.25    treated    (Aluminium    hydrate, stearic    acid)    Titanated Micas               0.1    0.1    0.1  0.25 1.0  0.0  0.1    Talc       3.38   4.5    6.0  0.7  0.7  0.7  3.38    Silica     0.6    4.25   6.0  4.25 0.6  0.6  0.6    Nylon      0.0    0.0    0.0  0.0  0.5  0.0  0.0    C.    Cyclomethicone/               1.85   1.5    1.85 5.0  1.0  1.0  1.85    dimethicone    copolyol (90:10)    D.    Yellow Iron               1.2    1.2    0.6  0.4  1.2  1.2  1.2    Oxide    Red Iron Oxide               0.49   0.6    0.6  0.49 0.49 0.2  0.6    Black Iron Oxide               0.16   0.1    0.24 0.1  0.1  0.24 0.24    Ultramarine Blue               0.0    0.0    0.0  0.1  0.0  0.0  0.0    Cyclomethicone               0.0    0.0    0.0  0.0  0.68 0.0  0.0    E.    Synthetic Wax               0.1    0.5    0.5  0.1  0.0  0.0  0.0    Arachidyl  0.3    0.0    0.0  0.3  0.5  0.3  0.3    behenate    Stearic Acid               0.0    0.0    0.0  0.0  0.0  0.0  2.5    Palmitic Acid               0.0    0.0    0.0  0.0  0.0  2.5  0.0    Silica (spheron               6.0    0.0    6.0  0.0  0.0  0.0  0.0    P1500)    F.    Trihydroxy-               0.3    0.3    1.5  1.5  0.0  0.0  0.0    stearin    Cyclomethicone               1.0    4.0    0.0  0.0  4.0  4.0  4.0    Beeswax    1.5    1.2    0.0  0.0  1.3  0.0  0.0    Abil WED9  0.0    3.0    0.0  0.0  0.0  0.0  0.0    G.    Ethylene   0.05   0.0    0.0  0.0  0.0  0.05 0.05    brassylate    BHT        0.05   0.0    0.0  0.0  0.0  0.05 0.05    H.    Deionized water               to 100    Ethanol    6      5.5    4.0  7    6.0  8.0  6.0    Salicylic acid               1      1      1    2    2    2    0.0    Azeleic acid               0.0    0.0    0.0  0.0  0.0  0.0    Propylene glycol               2.37   2.37   1.37 2.37 0.0  2.37 0.0    Dipropylene               6.0    5.0    6.5  7.00 8.0  6.0  5.0    glycol    Sodium chloride               0.5    0.5    0.5  0.5  0.5  0.5  1.0    Glycerine  4.5    5.0    10.0 5.0  5.0  10.0 15.0    Tetrasodium               0.05   0.05   0.05 0.1  0.1  0.1  0.01    EDTA    Triethanolamine               0.0    0.0    0.0  0.0  0.0  0.0  0.75    Allantoin  0.0    0.0    0.1  0.0  0.0  0.0  0.0    sunscreen  0.0    0.0    0.0  0.2  0.2  0.0  0.0    polyvinylpyrrolid-               1      2      1.5  1    1    1    2    one (Luviskol    K17)    Sodium citrate               0.3    0.3    0.0  0.2  0.4  0.3  0.4    Sodium     0.0    0.0    0.1  0.4  0.0  0.2  0.0    Tetraborate    pH of aqueous               2.9    2.8    2.9  3.2  3.0  2.9  3.1    phase    I.    Deionized Water               0.0    0.0    0.0  0.0  10.0 0.0  0.0    J.    Propylene Glycol               0.0    0.0    0.0  2.0  0.0  0.0  0.0    Xanthan Gum               0.0    0.0    0.0  0.08 0.0  0.0  0.0    K.    Essential Oils               0.0    0.0    0.0  0.20 0.0  0.0  0.0    Perfume Oil               0.0    0.25   0.0  0.20 0.0  0.0  0.0    Vitamin A  0.0    0.05   0.0  0.0  0.0  0.0  0.0    Palmitate    L.    Aloe Vera Gel               0.0    0.0    3.0  0.0  0.0  0.0  0.0    Chamomile  0.0    0.0    0.1  0.0  0.0  0.0  0.0    Extract    ______________________________________     *Contains about 1% propylene glycol.

The various components listed in the Table have been segregated intogroups, the constituents of each group being mixed together before beingadded to members of the remaining groups in accordance with theprocedures set forth below.

In the first step, the mixture of components of phase A is stirred forapproximately 5 minutes with sheer mixing until homogeneous. With highspeed sheer mixing, the materials of phase B are added gradually to Aand the batch is mixed for 20 minutes until dispersed.

The components of phase C and then phase D are slowly added to themixture of phases A and B with high shear mixing until dispersed. Silicais added at this point and dispersed through the mixture.

The resulting batch heated to 90° C. before the addition of thecomponents of phase E. The vessel is cooled to 55° C. and the premixedphase F is added. The batch is mixed until homogeneous. The mixture iscooled to 30° C. and phase G is added.

A premix of phase H is made by mixing all the components untilcompletely dissolved. At 30° C. the premix of phase H is added to thebatch mixture with high shear, ensuring that there is no excess water onthe surface. The mixture is then milled for 15 minutes.

Finally phases I, J, K, and L are added as diluent.

The resulting make-up composition is ready for packaging.

The make-up compositions of the Examples exhibit anti-acne activity andimproved formulation and colour stability.

We claim:
 1. A cosmetic composition in the form of a water-in-oil oroil-in-water emulsion comprising:a.) from about 0.1% to about 10% byweight of an acidic anti-acne active selected from the group consistingof salicylic acid, retinoic acid, azelaic acid, lactic acid, glycolicacid, pyruvic acid, flavonoids, and mixtures thereof dissolved in theaqueous phase; b.) from about 0.1% to about 10% by weight of apyrrolidone-based complexing agent; c.) from about 0.1 to about 25% byweight of a pigment or mixture of pigments dispersed in the oil phase;d.) from about 1% to about 50% by weight of silicone oil selected fromthe group consisting of volatile silicones, non-volatile silicones andmixtures thereof; e.) from about 0.1% to about 30% by weight of ahumectant selected from the group consisting of sorbitol, propyleneglycol, butylene glycol, hexylene glycol, glycerin, alkoxylated glucosederivatives, hexanetriol, glucose ethers, urea, D-panthenol,DL-panthenol, calcium pantothenate, royal jelly, panthetine,pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyllactose, vitamin B complex, polyglycerylmethacrylate lubricants having aviscosity of from about 300,000-1,100,000 cp at 25° C., and mixturesthereof; f.) from about 0.1% to about 10% by weight of a matte finishingagent selected from the group consisting of silica, hydrated silica,mica, talc, polyethylene, titanium dioxide, bentonite, hectorite,kaolin, chalk, diatomaceous earth, attapulgite, zinc oxide and mixturesthereof; and g.) from about 1% to about 15% by weight of an emollientwhich is a natural or synthetic oil selected from the group consistingof mineral oils, vegetable oils, animal oils) fats, waxes, fatty acidesters, fatty alcohols, alkylene glycol ethers, alkylene glycol esters,polyalkylene glycol ethers, polyalkylene glycol esters, fatty acids andmixtures thereofwherein the pigment or mixture of pigments is treatedwith a material selected from the group consisting of silicones,lecithin, lauroyl, collagen, polyethylene, amino acids and ester oils.2. A cosmetic composition according to claim 1 wherein the aqueous phasecomprising the anti-acne active dissolved therein is anaqueous/alcoholic solution of the anti-acne active having a pH of lessthan about pK_(a) +1, where pK_(a) is the logarithmic acidity constantfor the fully protonated anti-acne active.
 3. A make-up compositionaccording to claim 2 wherein the pyrrolidone-based complexing agent is apolyvinylpyrrolidone complexing agent.
 4. A cosmetic compositionaccording to claim 1 wherein said anti-acne active is selected from thegroup consisting of salicylic acid and azelaic acid and mixturesthereof.
 5. A cosmetic composition according to claim 1 additionallycomprising from about 0.01% to about 5% by weight of citric acid or saltthereof.
 6. A cosmetic composition according to claim 1 in the form of awater-in-oil emulsion.
 7. A cosmetic composition according to claim 1wherein the volatile silicone oil is selected from the group consistingof cyclic polyorganosiloxanes having viscosities of less than about 10centistokes and linear polyorganosiloxanes having viscosities of lessthan about 5 centistokes at 25° C., and mixtures thereof.
 8. A cosmeticcomposition according to claim 7, wherein the volatile silicone oil isselected from the group consisting of cyclic polydimethylsiloxaneshaving from 3 to 9 silicon and linear polydimethylsiloxanes having from3 to 9 silicon atoms.
 9. A cosmetic composition according to claim 1wherein the non-volatile silicone oil comprises apolydiorganosiloxane-polyoxyalkylene copolymer containing at least onepolydiorganosiloxane segment and at least one polyoxyalkylene segment.10. A cosmetic composition according to claim 9 wherein thepolydiorganosiloxane-polyoxyalkylene copolymer is dimethicone copolyol.11. A cosmetic composition according to claim 1 wherein the humectant isglycerine.
 12. A cosmetic composition according to claim 1 comprisingfrom about 0.1% to about 5% by weight of anti-acne active.
 13. Acosmetic composition according to claim 1 comprising from about 0.1% toabout 5% by weight of pyrrolidone-based complexing agent.
 14. A cosmeticcomposition according to claim 1 wherein the silicone oil comprises fromabout 2% to about 25% by weight of the composition of non-volatilesilicones.
 15. A cosmetic composition according to claim 1 comprisingfrom about 5% to about 25% by weight of composition of humectant.
 16. Acosmetic composition according to claim 1 wherein the cross-linkedhydrophobic copolymer is in the form of a lattice and wherein at leastone active ingredient is dispersed uniformly throughout and entrappedwithin the copolymer lattice, the active ingredient being selected fromthe group consisting of skin compatible oils, skin compatiblehumectants, emollients, moisturizing agents and sunscreens.
 17. Acosmetic composition according to claim 1 wherein the matte finishingagent is selected from the group consisting of silica and hydratedsilica.
 18. A cosmetic composition according to claim 1 wherein theemollient is selected from the group consisting of isopropyl palmitate,isopropyl isostearate, dioctyl maleate, propylene glycoldicaprylate/propylene glycol dicaprate, caprylic triglyceride/caprictriglyceride, squalane, mineral oil, cetearylisononanoate and lanolinalcohol, and mixtures thereof.
 19. A cosmetic composition according toclaim 1 wherein the oil phase comprises form about 0.1% to about 10% byweight of humectant on a composition basis.
 20. A cosmetic compositionaccording to claim 1 comprising from about 30% to about 95% by weight ofthe oil phase and from about 5% to about 70% by weight of the waterphase.
 21. A cosmetic composition according to claim 1 additionallycomprising one or more ultraviolet absorbing agents.